Devices and methods for hydrogen generation via ammonia decomposition

ABSTRACT

Systems and methods for hydrogen generation via ammonia decomposition that utilize a fixed bed reactor configured to receive inflows of NH3 and oxidant and to produce an outflow of high purity H2. The fixed bed reactor contains a fixed bed of a NH3 decomposition catalyst wherewith the NH3 decomposes to form N2 and H2; a plurality of ceramic hollows fibers with a high surface to volume ratio disposed in the fixed bed, the hollow fibers having an H2 selective membrane disposed thereon for extracting H2 from N2 and to form a permeate of the high purity H2 and a retentate of primarily N2; and a catalytic H2 burner also disposed in the fixed bed, the catalytic H2 burner for burning a portion of the H2 with the oxidant to provide thermal energy for the NH3 decomposition.

CROSS REFERENCE TO RELATED APPLICATION

This application claims the benefit of U.S. Provisional Patent Application, Ser. No. 62/541,962, filed on 7 Aug. 2017. The co-pending Provisional Application is hereby incorporated by reference herein in its entirety and is made a part hereof, including but not limited to those portions which specifically appear hereinafter.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

This invention was made with government support under grant DE-AR0000809 awarded by DOE/ARPA-E. The government has certain rights in the invention.

BACKGROUND OF THE INVENTION Field of the Invention

This invention relates generally to hydrogen generation and, more particularly, to hydrogen generation via ammonia decomposition including devices, systems and methods particularly suited therefore.

Description of Related Art

There is a need and demand for hydrogen generation from a carbon neutral liquid fuel (CNLF) with high yield and sufficient purity for use in commercial proton exchange membrane (PEM) fuel cells. Required metrics, set by the US Department of Energy (DOE) Advanced Research Projects Agency-Energy (APRA-E), for such hydrogen generation include:

-   -   Conversion to hydrogen>99%     -   H₂ generation rate>0.15 g/h/cm³     -   Energy efficiency>80%     -   Maximum NH₃ decomposition reactor temperature of 450° C.     -   Hydrogen delivered cost at target pressure (30 bar)<$4.5/kg

It is very challenging for existing NH₃ cracking technologies to meet these metrics due to a variety of facts and factors, including:

-   -   Low reaction temperature (<450° C.) and high NH₃ pressure (10˜15         bar) limit NH₃ conversion to less than 95%;     -   NH₃ decomposition is an endothermic reaction and thus requires         energy input; and     -   The cracked H₂ is mixed with N₂, which decreases the efficiency         of the PEM fuel cell. For example, with 60% dilution with N₂,         current density may decrease 8˜30% at 60° C.

Apollo Energy System Inc. (USA) designed an NH₃ cracking device to generate H₂ for fuel cells. H₂-containing anode off gas was used as a fuel for combustion to provide thermal energy for the cracker. Conversion to H₂ was high (99.99%) due to the high reactor temperature (480˜660° C.). The energy efficiency was not reported, but it is likely high due to the efficient use of thermal energy from H₂ combustion for reactor heating. An efficient commercial catalyst (70 wt % Ni on Al₂O₃) modified with Ru was used. Therefore, a high H₂ generation rate was also obtained. Membrane reactors have been studied for H₂ generation from NH₃ decomposition. However, the technology is still at the early research stage, and both the Hz generation rate and conversion to H₂ are much lower than ARPA-E's targets (see Table 1).

SUMMARY OF THE INVENTION

The present development is expected to solve at least some and preferably each of the above-identified intrinsic issues and desirably satisfy at least some and preferably each of the above-identified metrics.

The present development can be adopted for providing high purity H₂ at high rate and low cost from NH₃ decomposition for PEM fuel cell application as well as significantly reducing fuel transportation and storage cost. As detailed below, the subject novel compact membrane reactor also allows the use of NH₃ as an effective H₂ source for many other potential applications that utilize H₂ fuel. This may lead to entirely new markets. Furthermore, via this platform, NH₃ can be effectively coupled with maturing H₂ utilization technologies, allowing it becoming a new generation of fuel for wide applications.

Systems and methods in accordance with selected aspects of the subject development can advantageously employ a membrane reactor containing: a low-cost, highly active catalyst for NH₃ decomposition, an H₂ selective membrane on ceramic hollow fibers with high surface to volume ratio for extracting Hz from N₂ (simultaneously shifting NH₃ decomposition reaction), and a catalytic H₂ burner to provide thermal energy for NH₃ decomposition.

A system for generating hydrogen via ammonia decomposition in accordance with specific embodiment of the subject invention development desirably includes a fixed bed reactor configured to receive inflows of NH₃ and oxidant and to produce an outflow comprising high purity H₂. The fixed bed reactor includes or contains a fixed bed of a NH₃ decomposition catalyst wherewith the NH₃ decomposes to form N₂ and H₂; a plurality of ceramic hollows fibers with a high surface to volume ratio disposed in the fixed bed, the hollow fibers having an H₂ selective membrane disposed thereon for extracting H₂ from N₂ and to form a permeate comprising the high purity H₂ and a retentate comprising primarily N₂; and a catalytic H₂ burner also disposed in the fixed bed, the catalytic H₂ burner for burning a portion of the Hz with the oxidant to provide thermal energy for the NH₃ decomposition.

A method for generating hydrogen via ammonia decomposition in accordance with one aspect of the development involves introducing ammonia into such a membrane reactor so as to decompose at least a portion of the ammonia to form ammonia decomposition products including hydrogen gas and then separating at least a portion of the hydrogen gas from the decomposition products.

In one embodiment, a method for generating hydrogen via ammonia decomposition is provided that involves introducing and decomposing ammonia to form hydrogen and then separating and recovering high purity hydrogen via a specified fixed bed reactor system. More particularly, the fix bed reactor system includes a fixed bed membrane reactor that contains a fixed bed of a NH₃ decomposition catalyst for NH₃ decomposition to form N₂ and H₂. The reactor also includes a plurality of ceramic hollows fibers having a high surface to volume ratio disposed in the fixed bed. The hollow fibers have an H₂ selective membrane disposed thereon for extracting H₂ from N₂ and to form a permeate comprising high purity H₂ and a retentate comprising primarily N₂. The reactor further includes a catalytic H₂ burner also disposed in the fixed bed. The catalytic H₂ burner is adapted and effective for burning a portion of the H₂ to provide thermal energy for the NH₃ decomposition. Thus, the step of decomposing at least a portion of the ammonia is desirably achieved via the fixed bed of the NH₃ decomposition catalyst and thermal energy produced or provided by the catalytic H₂ burner to form ammonia decomposition products including H₂. The plurality of ceramic hollows fibers having a high surface to volume ratio disposed in the fixed bed desirably serve to and are effective to separate and recover high purity hydrogen from the decomposition products.

BRIEF DESCRIPTION OF THE DRAWINGS

Objects and features of this invention will be better understood from the following description taken in conjunction with the drawings, wherein:

FIG. 1 is a simplified schematic of a system for generating hydrogen via ammonia decomposition and more particularly a membrane reactor for H₂ generation via thermal catalytic NH₃ decomposition in accordance with one aspect of the subject development.

FIG. 2 is a photomicrograph of designated portion A shown in FIG. 1, e.g., low-cost, highly active Ru-based catalyst for NH₃ decomposition contained within the membrane reactor in accordance with one aspect of the subject development.

FIG. 3 is a simplified schematic representation of designated portion B shown in FIG. 1, e.g., showing an H₂ selective membrane on ceramic hollow fibers with high surface to volume ratio for extracting H₂ from N₂ (simultaneously shifting NH₃ decomposition reaction) in accordance with one aspect of the subject development.

FIG. 4 is a simplified schematic representation of designated portion C shown in FIG. 1, e.g., a catalytic H₂ burner to provide thermal energy for NH₃ decomposition in accordance with one aspect of the subject development.

FIG. 5 is a simplified schematic of an H₂ production test system in accordance with one aspect of the subject development and referenced in Example 1.

FIG. 6 is a simplified schematic of an HYSIS simulation system referenced in Example 2.

DETAILED DESCRIPTION

The subject development provides a novel compact intensive and modular NH₃ decomposition (2NH₃

N₂+3H₂) device with high conversion and high energy efficiency (>70%) at relatively low temperature (<450° C.).

An exemplary system or device in accordance with the subject development is expected to generate high purity H₂ at high rate from close-to-complete NH₃ conversion, in a small reactor volume.

A system or device for generating hydrogen via ammonia decomposition, generally designated by the reference numeral 10 and in accord with one embodiment of the subject development, is shown in FIG. 1. The system 10 includes a membrane reactor 12 that includes or comprises three key components: i) a fixed bed of low-cost, highly active catalyst for NH₃ decomposition, generally designated by the reference numeral 14 and more specifically shown in FIG. 2, ii) an H₂ selective membrane on ceramic hollow fibers with high surface to volume ratio, generally designated by the reference numeral 16, for extracting H₂ from N₂ and simultaneously shifting NH₃ decomposition reaction, more specifically shown in FIG. 3 and a catalytic H₂ burner to provide thermal energy for NH₃ decomposition, generally designated by the reference numeral 18 and more specifically shown in FIG. 4.

In these figures, certain of the process streams are identified as follows:

101 Feed—NH₃

102 Cracked stream—N₂+H₂ (−75%)

103 Product—H₂ (high purity)

104 Membrane retentate—N₂+H₂ (−25%)

105 Air—feed to the catalytic burner

106 Side product—N₂+H₂O

As shown in FIGS. 1-4, a feed stream of NH₃ 101 is introduced into the membrane reactor 12 such as through an inlet 22. In the reactor 12, the NH₃ contacts the NH₃ decomposition catalyst fixed bed 14 and undergoes decomposition/cracking to form nitrogen (N₂) and hydrogen (H₂) gas, see FIG. 2. The 142 selective membrane on ceramic hollow fibers with high surface to volume ratio 16 serve to separate or extract H₂ from N₂ from the cracked stream, stream 102, see FIG. 3, and form a stream 103 of high purity H₂ such as discharged or recovered from the reactor, such as via the product outlet 24. Suitable ceramic hollow fibers includes aluminum hollow fibers but other ceramic materials such as known to those in the art can be used, if desired. As shown, catalyst can desirably be loaded on the external surface of the hollow fibers 30. As shown in FIG. 3, the ceramic hollow fibers 30 in a dense tube 31, e.g., stainless steel tube, wherethrough the H₂ permeate is recovered, stream 103, and the membrane retentate is passed on, stream 104. As shown in FIG. 3, active catalyst 32 can also be loaded in the ceramic hollow fibers 30 to assist in the decomposition residual NH₃.

As noted above, the reactor 12 includes and/or contains a catalytic H₂ burner 18 such as to provide thermal energy for NH₃ decomposition. As shown in FIG. 4, the catalytic H₂ burner 18 can desirably be formed of or include a metal tube 40 such as containing a H₂ oxidizing catalyst 42, such as known in the art. As shown in FIG. 1 and FIG. 4, the catalytic H₂ burner 18 desirably serves to burn a portion of the produced H₂ (for example, such as hydrogen in the membrane retentate, stream 104 reacting with via intake oxidant, e.g., air, such as stream 105) to provide thermal energy for the NH₃ decomposition.

The subject development can and desirably does provide or result in the following advantages/characteristics:

-   -   Pressurized NH₃ vapor at 10˜15 bar (stream 101) will be used         directly as feedstock;     -   Low-cost, highly active catalysts (for example, ruthenium-based         NH₃ decomposition catalysts such as known in the art or other         suitable NH₃ decomposition catalysts such as known in the art)         will be used in a compact fixed bed reactor for high rate NH₃         decomposition (2NH₃         N₂+3H₂) at reaction temperature below 450° C.;     -   H₂ selective membrane on ceramic hollow fibers with high surface         to volume ratio will be used as a reactor boundary to extract         high purity H₂ from the reaction product; the removal of the H₂         will also shift the reaction towards higher conversion;     -   If needed, active catalyst will also be loaded in the ceramic         hollow fiber to decompose residual NH₃;     -   Lower concentration residual H₂ in the retentate (stream 104)         will be burned with air in a catalytic burner to provide thermal         energy uniformly needed for NH₃ decomposition;     -   Permeated high purity H₂ (stream 103) and exhaust from catalytic         H₂ combustion (stream 106) at elevated temperature will be used         to preheat NH₃ feed (stream 101); and     -   High purity H₂ (>99%) (stream 103) after heat exchange will be         compressed for applications.

Table 1, below, shows a comparison of the invention with current and emerging technologies for H₂ generation from thermocatalytic NH₃ decomposition and also with the ARPA-E technical targets.

TABLE 1 Comparison between technologies and ARPA-E technical performance targets Bimodal catalytic Apollo membrane Palladium Invention ARPA- Energy reactor membrane membrane Description E target System^([1]) (BCMR)^([3]) reactor^([4]) Reactor H₂ delivered cost at target <$4.5/kg N/A N/A N/A $4.078/kg pressure Final prototype size, L H₂/min 10 7.5 0.044 0.081 10 H₂ generation rate, g H₂/h/cm³ >0.15 0.126 0.038 0.0144 0.2 Conversion to H₂ >99% >99.99% 74%     85%  >99% Energy efficiency >80% N/A N/A N/A 88.45% Maximum cracking temperature, 450 480~660 400~450 500~600 450 ° C. H₂ delivered pressure, bar 30 1 0.005 1 30 Life time (projected), yrs 10 N/A N/A N/A 10 Concentration of catalyst <100 ppb <100 ppm^(a) NH₃ (4.5%) <0.8% <100 ppb poisoning impurities N/A: not available; ^(a)calculated based on reported conversion;

As identified above, Apollo Energy System Inc. (USA) designed an NH₃ cracking device to generate H₂ for fuel cell. Hz-containing anode off gas was used as a fuel for combustion to provide thermal energy for the cracker. Conversion to H₂ was high (99.99%) due to the high reactor temperature (480˜660° C.). The energy efficiency was not reported, but it is likely high due to the efficient use of thermal energy from H₂ combustion for reactor heating. An efficient commercial catalyst (70 wt % Ni on Al₂O₃) modified with Ru was used. Therefore, a high H₂ generation rate was also obtained. Membrane reactors have been studied for H₂ generation from NH₃ decomposition.^([9][10]) However, the technology is still at the early research stage, and both the H₂ generation rate and conversion to H₂ are much lower than ARPA-E's targets (Table 1).

HYSYS simulation/calculations (Examples 1 and 2) show that the subject development is expected to have high H₂ production rate, low H₂ delivered cost at target pressure, and high energy efficiency at 400° C., as shown in Table 1. The lower reaction temperature is expected to extend the lifetimes of both membrane and catalyst. NH₃ conversion is expected to be higher than 99% due to the equilibrium reaction shifting by selective H₂ extraction. Overall, compared with existing technologies, the subject development can or does result in the following advantages:

-   -   Rational and modular design of well-integrated catalyst,         membrane and H₂ burner;     -   High performance of three key components as supported by our         preliminary results;     -   Lower operation temperature (350-450° C.) while         close-to-complete NH₃ decomposition;     -   High H₂ purity (>99%); and     -   Higher energy efficiency and much smaller equipment size         (meaning smaller footprint).

Ammonia, as a promising CNLF and an effective H₂ source, can be synthesized from air and water (N₂ extracted from air and H₂ from water) using renewable energy sources. To produce H₂ as an intermediate, it is essential to develop effective and economic NH₃ decomposition technologies. The subject development (such as represented the system schematic shown in FIG. 1) represents a new and innovative solution. Its innovativeness is reflected in the following aspects:

-   -   Low-cost, highly active catalysts for fast NH₃ decomposition;     -   Low-cost highly H₂ selective membrane for extracting H₂ with         purity >99% (simultaneously shifting NH₃ decomposition reaction         towards conversion >99%);     -   Catalytic H₂ burner embedded in the reactor for providing         thermal energy for NH₃ decomposition to achieve overall energy         efficiency as high as 88%; and     -   Membrane in a high packing-density (high surface to volume         ratio) hollow fiber configuration capable of achieving a compact         modular system that can be scaled up linearly by just adding         additional membrane modules.

The present invention is described in further detail in connection with the following examples which illustrate or simulate various aspects involved in the practice of the invention. It is to be understood that all changes that come within the spirit of the invention are desired to be protected and thus the invention is not to be construed as limited by these examples.

EXAMPLES Example 1 Calculation of H₂ Production Rate in the Membrane Reactor

FIG. 5 illustrates an Hz production test system 500 in accordance with one aspect of the subject development. The system 500 includes a NH₃ supply source such as an NH₃ cylinder 502, a membrane reactor 504 system such as described above, and a hydrogen product storage, such as a hydrogen product tank 506. The system 500 further include a preheater cross heat exchanger 510 and a cross heat exchanger 512 such as to appropriately preheat the feed (e.g., stream 101) to the membrane reactor 502 and to recover heat from the hydrogen product (stream 103) and the reactor flue gas (stream 106), respectively.

The system 500 shows the NH₃ feed stream (stream 101 at 25° C., 10 bar and a feed rate of 0.3434 mol/min), permeate stream (stream 103 at 400° C., 2.5 bar, the permeate composed of H₂ at 0.4464 mol/min=10 L/min and N₂ at 0.004509 mol/min), and retentate stream (stream 104 at 400° C., 2.5 bar, the retentate composed of that 0.0687 mol/min and N₂ at 0.1673 mol/min) and the membrane reactor 504 operating at 400° C.

H₂ production rate: 10 L H₂/min

Input:

Catalyst:

K-promoted Ru/γ-Al₂O₃

Catalytic activity at 400° C.: 4.5 mmol H₂/min/g catalyst

Packing density: 1 g/cm³

Membrane:

Composite SAPO-34 membrane on hollow fiber (1.5 mm od) housed in metal tube (2 mm od×1.6 mm id)

H₂ permeance at 400° C.: 1.5×10⁴ mol/(m²·s·Pa)

H₂/N₂ selectivity: >700

Catalytic H₂ burner:

Pt-impregnated Ni foam

Heat transfer rate: 1.5 kcal/(cm²·h)

Output:

Catalyst volume: 116 cm³

Membrane area: 0.2 m²

Membrane volume: 133 cm³

Catalytic H₂ burner volume: 10 cm³ (estimated from energy needed for decomposing NH₃ feed)

Estimated top space of the membrane reactor: 10 cm³

Total membrane reactor volume: 269 cm³

Calculated H₂ generation rate: 0.20 g H₂/h/cm³

Example 2 Energy Efficiency Calculation Using HYSYS Simulation

Referencing the HYSIS simulation system 600 shown in FIG. 6.

HYSYS flow diagram:

Stream and energy summary:

H₂ production: 10 L (STP)/min and at delivery pressure of 30 bar

${{Energy}\mspace{14mu} {{Efficiency}\left( {E\; E} \right)}} = {\frac{P}{P + E} = {\frac{0.0271 \times 2 \times 33.3}{{0.0271 \times 2 \times 33.3} + {848.7018/3600}} = {88.45\%}}}$

While in the foregoing detailed description this invention has been described in relation to certain preferred embodiments thereof, and many details have been set forth for purposes of illustration, it will be apparent to those skilled in the art that the invention is susceptible to additional embodiments and that certain of the details described herein can be varied considerably without departing from the basic principles of the invention. 

What is claimed includes:
 1. A method for generating hydrogen via ammonia decomposition, the method comprising: introducing ammonia into a system comprising: a fixed bed membrane reactor containing; a fixed bed of a NH₃ decomposition catalyst for NH₃ decomposition to form N₂ and H₂; a plurality of ceramic hollows fibers with a high surface to volume ratio disposed in the fixed bed, the hollow fibers having an H₂ selective membrane disposed thereon for extracting H₂ from N₂ and to form a permeate comprising high purity H₂ and a retentate comprising primarily N₂; and a catalytic H₂ burner also disposed in the fixed bed, the catalytic H₂ burner for burning a portion of the H₂ to provide thermal energy for the NH₃ decomposition; decomposing at least a portion of the ammonia via the fixed bed of the NH₃ decomposition catalyst and thermal energy produced by the catalytic H₂ burner to form ammonia decomposition products including H₂; and separating at least a portion of the H₂ from the decomposition products.
 2. The method of claim 1 wherein the ammonia introduced into the system comprises NH₃ vapor at 10-15 bar.
 3. The method of claim 1 wherein the separating at least a portion of the H₂ from the decomposition products comprises forming a permeate comprising the high purity H₂.
 4. The method of claim 3 additionally comprising: forming a retentate stream containing primarily N₂ and residual H₂ and wherein at least a portion of the residual H₂ is burned with air in the catalytic burner to provide thermal energy for the NH₃ decomposition.
 5. The method of claim 1 wherein the maximum temperature of the fixed bed membrane reactor is no more than 450° C.
 6. The method of claim 1 wherein the conversion to hydrogen is in excess of 99%.
 7. The method of claim 1 additionally comprising cracking residual NH₃ via a NH₃ cracking catalyst loaded on the ceramic hollows fibers.
 8. The method of claim 1 wherein the NH₃ decomposition catalyst comprises a Ru-based catalyst.
 9. The method of claim 1 additionally comprising: preheating the ammonia introduced into the system with heat provided by at least one stream selected from the group consisting of a stream of permeated high purity H₂ and a stream of catalytic H₂ combustion exhaust.
 10. A system for generating hydrogen via ammonia decomposition, the system comprising: a fixed bed reactor configured to receive inflows of NH₃ and oxidant and to produce an outflow comprising high purity H₂, the fixed bed reactor containing; a fixed bed of a NH₃ decomposition catalyst wherewith the NH₃ decomposes to form N₂ and H₂; a plurality of ceramic hollows fibers with a high surface to volume ratio disposed in the fixed bed, the hollow fibers having an H₂ selective membrane disposed thereon for extracting H₂ from N₂ and to form a permeate comprising the high purity H₂ and a retentate comprising primarily N₂; and a catalytic H₂ burner also disposed in the fixed bed, the catalytic H₂ burner for burning a portion of the H₂ with the oxidant to provide thermal energy for the NH₃ decomposition.
 11. The system of claim 10 wherein the retentate additionally comprises H₂ and wherein at least a portion of the retentate and the oxidant inflow into the fixed bed reactor are introduced into the catalytic H₂ burner to provide thermal energy for the NH₃ decomposition.
 12. The system of claim 10 wherein the catalytic H₂ burner comprises a metal tube containing a H₂ oxidizing catalyst.
 13. The system of claim 10 additionally comprising a NH₃ cracking catalyst loaded on the ceramic hollows fibers for residual NH₃ cracking.
 14. The system of claim 10 providing a conversion to hydrogen in excess of 99%.
 15. The system of claim 10 wherein the maximum NH₃ decomposition reactor temperature is no more than 450° C.
 16. The system of claim 10 wherein the inflow of NH₃ comprises NH₃ vapor at 10-15 bar.
 17. The system of claim 10 wherein the conversion to hydrogen is in excess of 99%.
 18. The system of claim 10 additionally comprising a preheater whereby heat provided by at least one stream selected from the group consisting of a stream of permeated high purity H₂ and a stream of catalytic H₂ combustion exhaust preheats the inflow of NH₃ to the reactor. 